ENGINEERING CHEMISTRY

UNIT-I
MOLECULAR STRUCTURE AND SPECTROSCOPIC TECHNIQUES

1.1. INTRODUCTION:-
Atom:-
An Atom is a small part of element that takes part in chemical reactions. It is made up
of three subatomic structures called Protons, Neutrons, and Electrons.The Nucleus, in the
center of the atom, consists of protons and neutrons and is surrounded by electrons.
Molecule:-
A group of two or more than two atoms of the same or different elements that are
chemically bonded together is called a molecule.
Orbital:-
An Orbital is a three dimensional space around nucleus where the probability of
finding an electron is high. They represent the probability of finding an electron in any one
place. They correspond to different energies. So an electron in an orbital has definite energy.
1.2. Quantum numbers
Quantum numbers are the numbers which are used to describe completely the state of
electrons in an atom. (or)
The set of numbers used to describe the position and energy of the electron in an atom
are called quantum numbers.
Four types of quantum numbers
1. Principal quantum number
2. Azimuthal quantum number
3. Magnetic quantum number
4. Spin quantum number
1.Principal quantum number
 It describes the size and energy level or shell of electron in an atom . It is denoted by ‘n’.
 Also describe the distance between the electron and the nucleus i.e., larger the value of
principal quantum number, greater the distance between electron and the nucleus.
 The value of the principal quantum number might be greater than or equal to one. i.e., n
= 1,2,3,….
 The value n=1 denotes the innermost electron shell of an atom, which corresponds to the
lowest energy state of an electron and as the n value increases the energy level increases.

2.The azimuthal quantum number

 It describes the sub energy level or sub shell of the electron in an atom and also describe
the shape of the electron clouds around the nucleus of an atom. It is denoted by ‘�’.
 This value depends on the value of the principal quantum number, i.e. the value of the
azimuthal quantum number ranges between 0 and (n-1).

Dr. KISHOR PALLE DEPT. OF CHEMISTRY ANURAG UNIVERSITY

 For example, if n =3, the azimuthal quantum number are 0,1 and 2. When � =0, the
resulting sub shell is an ‘s’ sub shell. Similarly, when �=1 and �=2, the resulting sub shells
are ‘p’ and ‘d’ sub shells (respectively). Therefore, when n=3, the three possible subshells
are 3s, 3p, and 3d.
3.Magnetic quantum number
 It describes the total number of orbitals in a sub shell and the orientation of these orbitals.
It is denoted by ‘m’.
 The value of the magnetic quantum number is dependent on the value of the azimuthal
quantum number.
 For a given value of �, the value of m ranges between the interval -� to +�. • For example,
if � = 1 in an atom, the possible values of the magnetic quantum number are -1, 0, +1 and
the orbitals are named as px, py and pz.
4.Electron spin quantum number
 The electron spin quantum number describe the spinning nature of the electron which
are revolving around the nucleus of an atom. It is denoted by ‘s’
 The possible values of the electron spin quantum number are +½ and -½.
 The positive value of s implies an upward spin on the electron which is also called ‘spin
up’ and is denoted by the symbol ↑.
 The negative value of s implies a downward spin on the electron which is also called
‘spin down’ and is denoted by the symbol ↓.
1.3.Atomic orbitals:-
Atomic orbitals are regions of space around the nucleus of an atom where an electron
is likely to be found. Atomic orbitals allow atoms to make covalent bonds. An atomic orbital
can have a maximum of two electrons. Atomic orbitals are labelled as s, p, d, and f sub levels.
Each orbital is denoted by a number and a letter. The number denotes the energy
level of the electron in the orbital. Thus 1 refers to the energy level closest to the nucleus; 2
refers to the next energy level further out, and so on. The letter refers to the shape of the
orbital. The letters go in the order s, p, d, f, g, h, i, j, etc. Atomic orbitals s,p,d and f have fixed
shapes.
1.4.Shapes of orbitals
The Shape of s Orbitals

 ‘s’ orbitals are spherically symmetric having the probability of finding the electron at
a given distance equal in all the directions. It holds a maximum of two electrons.
 The size of the s’’ orbital is also found to increase with the increase in the value of the
principal quantum number (n), thus, 4s > 3s> 2s > 1s.

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The Shape of p Orbitals
The p orbital is dumbbell shaped and can hold up to six electrons. It has three sub
energy levels. These are given the symbols px, py and pz. The p orbitals at the second energy
level are called 2px, 2py and 2pz. There are similar orbitals at subsequent levels: 3px, 3py, 3pz,
4px, 4py, 4pz and so on.

 Similar to s orbitals the size, and energy of p orbitals increase with an increase in the
principal quantum number (4p > 3p > 2p).

The Shape of d Orbitals

 The magnetic orbital quantum number for d orbitals is given as (-2,-1,0, 1,2). Hence,
we can say that there are five d-orbitals.
 These orbitals are designated as dxy, dyz, dxz, dx2–y2 and dz2.
 Out of these five d orbitals, the shapes of the first four d-orbitals are similar to each
other, which is different from the dz2 orbital whereas the energy of all five d orbitals
is the same.

Dr. KISHOR PALLE DEPT. OF CHEMISTRY ANURAG UNIVERSITY

1.1.1.2.Molecular orbitals:-
 Molecular orbitals found in molecules.So, atomic orbitals join together to form molecular
orbitals.
 When two atoms move closer together to form a molecule, atomic orbitals overlap and
combine to become molecular orbitals.
 Molecular orbitals are regions around molecules where electrons are most likely to be
found.
 The number of newly formed molecular orbitals is equal to the number of combined
atomic orbitals. The molecular orbital surrounds the two nuclei of the atoms, and
electrons can move around both nuclei. Similar to atomic orbitals, molecular orbitals
maximally contain 2 electrons, which have opposite spins. Molecular orbitals are of two
types, bonding molecular orbitals and anti-bonding molecular orbitals. Bonding
molecular orbitals contain electrons in the ground state and anti-bonding molecular
orbitals contain no electrons in the ground state.
 Electrons may occupy in the anti-bonding orbitals if the molecule is in the excited state.
 Molecular orbitals can change their shapes depending on the hybridisation they are in.

1.1.2.Shapes of Atomic and Molecular orbitals:-

1. If two atomic orbitals overlap along the internuclear axis ,the molecular orbital formed is
called σ molecular orbital.

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2. If two atomic orbitals overlap sideways, the molecular orbital formed is called π
molecular orbital.
3. s orbitals are spherically symmetrical ,their wave function has the same size in all the
directions.
4. In p- orbital, one lobe is given a + sign and the other a – sign.
5. Overlapping of + part of the electron cloud of one atom with + part of the electron cloud
of second atom implies addition of the atomic orbitals leading to the formation of
bonding molecular orbitals.
6. The overlap of + part of the electron cloud of one atom with – part of the electron cloud
of the second atom means the subtraction of the atomic orbitals leading to the formation
of antibonding molecular orbital.

1s with 1s

2px with 2px and 2py with 2py

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2pz with 2pz
Taking Z-axis as the internuclear axis, the molecular orbitals formed are:

1.2.Molecular Orbital Theory:-

The Valence Bond Theory fails to answer certain questions like why He2 molecule
does not exist and why O2 is paramagnetic. Therefore in 1932 F. Hund and R.S. Mulliken
came up with Molecular Orbital Theory to explain
i. The formation of chemical bond
ii. Relative bond strengths
iii. Paramagnetic (or) Diamagnetic nature,etc. of molecules.
Molecular orbital theory (MOT) is a method for determining molecular structure in
which electrons are not assigned to individual bonds between atoms, but are treated as
moving under the influence of the nuclei in the whole molecule.
Salient features of the theory:-
1. According to the Molecular Orbital Theory, atomic orbitals of individual atoms combine
to form molecular orbitals. As a result of this,the atomic orbitals lose their identity.
2. Each and every electron in the molecular orbital belongs to all the nuclei of the
molecules.
3. Atoms have atomic orbitals with one nuclei and Molecules have molecular orbitals with
n nuclei. Thus, atoms are monocentric while molecules are polycentric.
4. The number of Molecular Orbital(M.O.) formed is equal to the number of overlapping
atomic orbitals.
5. Maximum capacity of a molecular orbital is two electrons with opposite spins..
6. Only atomic orbitals have comparable energies as well as proper orientations can
combine to form Molecular Orbital(M.O.).

Dr. KISHOR PALLE DEPT. OF CHEMISTRY ANURAG UNIVERSITY

 We know that we can consider electrons as either particle or wave nature. Therefore,
we can describe an electron in an atom as occupying an atomic orbital, or by a wave
function Ψ. These are solutions to the Schrodinger wave equation. Electrons in a molecule
occupy molecular orbitals. We can obtain the wave function of a molecular orbital by the
following methods.
 Linear Combination of Atomic Orbitals (LCAO)
 United Atom Method
1.2.1.Linear Combination of Atomic Orbitals (LCAO):-
As per this method, the formation of orbitals is because of Linear Combination
[addition(constructive) or subtraction(constructive)] of atomic orbitals which combine to
form the molecule. Consider two atoms A and B which have atomic orbitals described by the
wave functions ΨA and ΨB.
If the electron cloud of these two atoms overlaps, then we can obtain the wave
function for the molecule by a linear combination of the atomic orbitals ΨA and ΨB. The
below equation forms two molecular orbitals.
ΨMO = ΨA ± ΨB
Therefore, the combination of two atomic orbitals results in the formation of two
molecular orbitals. They are the bonding molecular orbital (BMO) and the anti-bonding
molecular orbital (ABMO).
1.2.1.1.Bonding Molecular Orbitals:-
When the addition of wave function takes place, the type of molecular orbitals formed
are Bonding Molecular Orbitals. We can represent constructive interaction by
ΨMO = ΨA + ΨB
They have lower energy than atomic orbitals involved.
1.2.1.2.Anti-Bonding Molecular Orbitals:-
When molecular orbital forms by the subtraction of wave function, the type of molecular
orbitals formed are anti-bonding Molecular Orbitals. We can represent destructive interaction
as
Dr. KISHOR PALLE DEPT. OF CHEMISTRY ANURAG UNIVERSITY
 ΨMO = ΨA – ΨB.
They have higher energy than atomic orbitals.
1.2.1.3.Non-Bonding Molecular orbitals:-
The molecular orbitals which do not take part in bond formation are called Non-Bonding
Molecular orbitals.
1.2.1.4.Relative Energies of Molecular Orbitals:-
 Bonding Molecular Orbitals (BMO) – Energy of Bonding Molecular Orbitals is less
than that of Anti Bonding Molecular Orbitals. This is because of the increase in the
attraction of both the nuclei for both the electron (of the combining atom).
 Anti-Bonding Molecular Orbitals (ABMO) – Energy of Anti Bonding Molecular
Orbitals is higher than Bonding Molecular Orbitals. This is because the electron tries
to move away from the nuclei and are in a repulsive state.
1.2.1.5..Rules for Filling of Molecular Orbitals
We have to follow certain rules while filling up molecular orbitals with electrons in
order to write correct molecular configurations. They are
 Aufbau Principle – This principle states that those molecular orbitals which have the
lowest energy are filled first.
 Pauli’s Exclusion Principle – According to this principle, each molecular orbital can
accommodate a maximum of two electrons having opposite spins.
 Hund’s rule- Pairing of electrons in the degenerate molecular orbital does not
occur,until each of them has one electron each.
1.2.1.6. Magnetic character:-
If a molecule contains one or more unpaired electrons in it molecular orbitals(M.Os.), it
is paramagnetic in nature; otherwise diamagnetic. Greater the number of unpaired eletcrons
in M.Os. of a substance,higher is its paramagnetic character.
1.3.Molecular orbitals of diatomic molecules:-
For a diatomic molecule, the atomic orbitals of one atom are shown on the left, and those
of the other atom are shown on the right. Each horizontal line represents one orbital that can
hold two electrons. The molecular orbitals formed by the combination of the atomic orbitals
are shown in the center. Dashed lines show which of the atomic orbitals combine to form the
molecular orbitals. For each pair of atomic orbitals that combine, one lower-energy (bonding)
molecular orbital and one higher-energy (antibonding) orbital result. Thus we can see that
combining the six 2p atomic orbitals results in three bonding orbitals (one σ and two π) and
three antibonding orbitals (one σ* and two π*).
We predict the distribution of electrons in these molecular orbitals by filling the orbitals
in the same way that we fill atomic orbitals, by the Aufbau principle. Lower-energy orbitals
fill first, electrons spread out among degenerate orbitals before pairing, and each orbital can
hold a maximum of two electrons with opposite spins (Figure). Just as we write electron
configurations for atoms, we can write the molecular electronic configuration by listing the
orbitals with superscripts indicating the number of electrons present.

Dr. KISHOR PALLE DEPT. OF CHEMISTRY ANURAG UNIVERSITY

1.5.Molecular orbital energy level diagrams:-
Molecular orbital diagram:
 The molecular orbital diagram describes the chemical bonding in a molecule based on
molecular orbital theory (MOT) and linear combination of atomic orbital(LCAO).
 The molecular orbital diagram has molecular orbital energy level at centre and is
surrounded by atomic orbital energy level.
 It shows electrons in both bonding and anti-bonding molecular orbital.
1.4.1.N2 Molecule:-
Each nitrogen atom have 7 electrons,so N2 molecule has total of ‘14’ electrons.
Hence N2 molecular orbital configuration is
σ1s2σ*1s2σ2s2σ*2s2π2px2=π2py2σ2pz2

Number of electrons in the bonding orbital=10

Number of electrons in the anti-bonding orbital=4
1
Bond order = 2 [NB − NA]

where, NB=number of bonding electrons, NA=number of anti-bonding electrons

Dr. KISHOR PALLE DEPT. OF CHEMISTRY ANURAG UNIVERSITY

 1 1
=2 (10-4)=2 × 6=3

Hence, bond order of O2 is 3.

N2 molecules are diamagnetic, because no unpaired electrons present in their molecular
orbitals.
1.4.1.O2 Molecule:-
Each Oxygen atom have 8 electrons, so O2 molecule has total of ‘16’ electrons.
Hence O2 molecular orbital configuration is
σ1s2σ*1s2σ2s2σ*2s2σ2pz2π2px2=π2py2π*2px1=π*2py1

Number of electrons in the bonding orbital=10

Number of electrons in the anti-bonding orbital=6
1
Bond order = 2 [NB − NA]

where, NB=number of bonding electrons, NA=number of anti-bonding electrons

1 1
=2 (10-6)=2 × 4=2

Dr. KISHOR PALLE DEPT. OF CHEMISTRY ANURAG UNIVERSITY

Hence, bond order of O2 is 2.
O2 molecules are paramagnetic, because of the presence of unpaired electrons in their
molecular orbitals.
1.4.1.F2 Molecule:-
Each Fluorine atom have 9 electrons, so F2 molecule has total of ‘18’ electrons.
Hence F2 molecular orbital configuration is
σ1s2σ*1s2σ2s2σ*2s2σ2pz2π2px2=π2py2π*2px2=π*2py2

Number of electrons in the bonding orbital=10

Number of electrons in the anti-bonding orbital=8
1
Bond order = 2 [NB − NA]

where, NB=number of bonding electrons, NA=number of anti-bonding electrons

1 1
=2 (10-8)=2 × 2=1

Hence, bond order of F2 is 1.

Dr. KISHOR PALLE DEPT. OF CHEMISTRY ANURAG UNIVERSITY

F2 molecules are diamagnetic, because no unpaired electrons present in their molecular
orbitals.
1.5. Pi-molecular Orbitals of Butadiene and Benzene
1.5.1. 1,3-Butadiene:

 Pi molecular orbitals are formed by the combination of π molecular orbitals of

two ethene molecules. This requires that we make an in-phase and an out-of-phase
combination for both the π and π* of ethene.

 This diagram represents the relative energies of pi molecular orbitals of 1,3-Butadiene

which is a derived compound of ethene.
 Each p orbital contributes one electron, resulting in the arrangement of four electrons
from four p-orbitals which combine in four different ways and form four molecular
orbitals designated by π1, π2, π3*, π4*.
Dr. KISHOR PALLE DEPT. OF CHEMISTRY ANURAG UNIVERSITY
 The number of nodes between p-orbitals increases by one for each successive energy
level, therefore the highest energy orbital has (n-1) nodes.
 π1 has three bonding interactions between C1-C2, C2-C3 and C3-C4. It has zero nodes
 π2 has two bonding interactions between C1-C2 and C3-C4 and one anti-bonding
interaction between C2-C3. It has one node between C2-C3. It is the highest occupied
molecular orbital (HOMO).
 π3* has one bonding interactions between C2-C3 and two anti-bonding interactions
between C1-C2 and C3-C4. It has two nodes between C1-C2 and C3-C4. It is the lowest
unoccupied molecular orbital (LUMO).
 π4* has three anti-bonding interactions between C1-C2, C2-C3 and C3-C4. It has three
nodes between C1-C2, C2-C3 and C3-C4.

Among these four orbitals π1 and π2 are bonding molecular orbitals and π3* and π4* are ant-
bonding molecular orbitals. The two bonding molecular orbitals are lower in energy than p-
orbitals, whereas two anti-bonding molecular orbitals are higher in energy than p-orbitals.
The energy in molecular orbitals increases with the rise in the number of nodes.

1.5.2. Benzene:

Benzene has a planar hexagonal structure in which all the six carbon atoms are sp2
hybridized. Four valency electrons of each carbon atom, three forms covalent bonds with
two carbon atoms and one hydrogen atoms. The remaining cyclic six p-orbitals(one on each
carbon) overlap to generate six molecular orbitals designated as π1, π2, π3, π4* π5* and π6*, in
which first three π1, π2, and π3 are bonding and remaining three π4* π5* and π6* are anti-
bonding.

Dr. KISHOR PALLE DEPT. OF CHEMISTRY ANURAG UNIVERSITY

 π1 Molecular orbital: π1 MO is the lowest-energy orbital. It has zero nodes between the p
atomic orbitals. π1 MO has six bonding interactions and zero anti-bonding interactions.
 π2 & π3 Molecular orbitals: π2 and π3 Mos are degenerate molecular orbitals (means same
energy orbitals) and each has one nodal plane. π2 has four bonding interactions and two
anti-bonding interactions. π3 has two bonding interactions and two anti-bonding
interactions.
 π4*& π5*Molecular orbitals: π4* and π5* are degenerate molecular orbitals and have two
nodal planes. π4* has two bonding interactions and four anti-bonding interactions. π5* has
zero bonding interactions and four anti-bonding interactions.
 π6* Molecular orbitals: π6* MO has three nodal planes. It has zero bonding interactions
and six anti-bonding interactions.
 Benzene has 6 π electrons which are filled in π1, π2 and π3 molecular orbitals.
 The highest occupied molecular orbital (HOMO) is π2 and π3 in benzene & the lowest
unoccupied molecular orbital (LUMO) is π4*and π5* in benzene.

Dr. KISHOR PALLE DEPT. OF CHEMISTRY ANURAG UNIVERSITY

 SPECTROSCOPIC TECHNIQUES
1.2.1.INTRODUCTION
Spectroscopy:
It is the branch of science that deals with the study of interaction of matter with light or
electromagnetic radiation.
1.2.2.ELECTROMAGNETIC SPECTRUM:-
Electromagnetic spectrum or EM spectrum is the range of all types of electromagnetic
radiation. The distribution of the radiation is based on their wavelength and frequency. The
waves that have shorter wavelength are more energetic while the waves with longer
wavelength are less energetic. Based on wavelength and frequency, the spectrum is divided
into seven electromagnetic waves. They are measured in Hertz.

Comparison of wavelength, frequency and energy for the electromagnetic spectrum.

Types of Electromagnetic Waves:-

Following is the list of types of electromagnetic waves:

Gamma rays: These are part of electromagnetic spectrum which includes visible as well as
invisible radiations and their wavelength is below 0.01nm. These have the highest frequency
which is greater than 10 Hz.
X-rays: These are parts of the electromagnetic spectrum and their wavelength is in the range
0.01nm to 10nm. They find applications in healthcare industry.
Ultraviolet (UV) rays: These are the part of electromagnetic spectrum with wavelength
between 10nm to 400nm. When there is a continuous exposure of the skin to these rays, they
tans skin and create burns. These will be produced by hot materials in space.
Visible light: These are part of the electromagnetic spectrum which lies between UV rays and
infrared rays. The wavelengths of these light are 400nm to 750nm. These are generated by
light bulbs.
Infrared radiation: These are the part of electromagnetic spectrum and their wavelength
range is between 750nm to 1mm. These are also referred to as thermal waves as they have
heat inducing property.

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Microwaves: These are part of electromagnetic spectrum and is known as microwave
radiation. Their wavelength range is between 1mm to 1m. In the electromagnetic spectrum
series, microwaves is between infrared radiation and radio waves.
Radio waves: These are part of electromagnetic spectrum and have the longest wavelengths
and huge band of frequencies. Their wavelength is greater than 1m. They find applications in
radio communication, broadcasting etc.
1.2.3.UV SPECTROSCOPY: -
UV spectroscopy is an important tool in analytical chemistry. The other name of UV
(Ultra-Violet) spectroscopy is Electronic spectroscopy as it involves the promotion of the
electrons from the ground state to the higher energy or excited state.
Introduction to UV spectroscopy
UV spectroscopy is type of absorption spectroscopy in which light of ultra-violet region
(10nm-400nm) is absorbed by the molecule. Absorption of the ultra-violet radiations results
in the excitation of the electrons from the ground state to higher energy state. The energy of
the ultra-violet radiation that are absorbed is equal to the energy difference between the
ground state and higher energy states ( ∆E = hυ).
Principle of UV spectroscopy
Any molecule has either n, π or σ or a combination of these electrons. These bonding (σ
& π) and non-bonding (n)electrons absorb the characteristic radiation and undergoes
transition from ground state to excited state.
By the characteristic absorption peaks, the nature of the electrons presents and hence the
molecular structure can be elucidated.
 When the molecule absorbs ultraviolet or visible light, its electrons get promoted
from the ground state to the higher energy state.
 In the ground state, the spins of the electrons in each molecular orbital are essentially
paired.
 In the higher energy state, if the spins of the electrons are paired, then it is called an
excited singlet state.
 On the other hand, if the spins of the electrons in the excited state are parallel, it is
called an excited triplet state.
 The triplet state is always lower in energy than the corresponding excited singlet state.
 Therefore, triplet state is more stable as compared to the excited singlet state.
 An excited singlet state is converted to excited triplet state with the emission of
energy as light.
 The higher energy states are designated as high energy molecular orbitals and also
called antibonding orbitals.
 Energy absorbed in the ultraviolet region produces changes in the electronic energy of
the molecule resulting from transition of valence electrons in the molecule.
 Three distinct types of electrons are involved organic molecule. These are as follows
῾σ᾽ electrons, ῾π᾿ electrons, ῾n᾿electrons.

Dr. KISHOR PALLE DEPT. OF CHEMISTRY ANURAG UNIVERSITY

 The electrons in a molecule can be of one of three types: namely σ (single bond), π
(multiple-bond), or non-bonding (n- caused by lone pairs). These electrons when imparted
with energy in the form of light radiation get excited from the highest occupied molecular
orbital (HOMO) to the lowest unoccupied molecular orbital (LUMO) and the resulting
species is known as the excited state or anti-bonding state.
1. σ-bond electrons have the lowest energy level and are the most stable electrons. These
would require a lot of energy to be displaced to higher energy levels. As a result these
electrons generally absorb light in the lower wavelengths of the ultraviolet light and
these transitions are rare.
2. π-bond electrons have much higher energy levels for the ground state. These electrons
are therefore relatively unstable and can be excited more easily and would require lesser
energy for excitation. These electrons would therefore absorb energy in the ultraviolet
and visible light radiations.
3. n-electrons or non-bonding electrons are generally electrons belonging to lone pairs of
atoms. These are of higher energy levels than π-electrons and can be excited by
ultraviolet and visible light as well.
From the Beer-Lambert law it is clear that greater the number of molecules capable of
absorbing light of a given wavelength, the greater the extent of light absorption. This is the
basic principle of UV spectroscopy.
Types of Transitions:-
In U.V spectroscopy molecule undergo electronic transition involving σ, π and n
electrons.Four types of electronic transition are possible.
i. σ ⇾ σ* transition
ii. π ⇾ π* transition
iii. n ⇾ σ* transition
iv. n ⇾ π* transition

i. σ ⇾ σ* Transition:-
 An electron in a bonding σ orbital of a molecule is excited to the corresponding anti-
bonding orbital by the absorption of radiation.
 To induce a σ ⇾ σ* transition it requires large energy.
Ex: Methane(CH4) contain only single C-H bonds it undergo only σ ⇾ σ* transition only, it
gives absorption maximum at 125nm.
Dr. KISHOR PALLE DEPT. OF CHEMISTRY ANURAG UNIVERSITY
ii.π ⇾ π* transitions
 π electron in a bonding orbital is excited to corresponding anti-bonding π*.
 Compounds containing multiple bonds like alkenes, alkynes, carbonyl,aromatic
compounds,etc undergo π ⇾ π* transitions.
Ex:- Alkenes generally absorb in the region 170 to 205 nm.
iii. n⇾ σ* transition:-
 Saturated compounds containing atoms with lone pair of electrons like O,N,S and
halogens are capable of n ⇾ σ* transition.
 It require less energy than the σ ⇾ σ* type.
 Most of the absorption peaks appearing below 200nm.
 In the presence of polar solvents the absorption maximum tend to shift shorter
wavelength.
Ex: Water , ethanol.In this the peaks in U.V region relatively small.
iv. n ⇾ π* transitions
 An electron from non-bonding orbital is promoted to anti-bonding π* orbital.
 Compounds containing double bond involving hetero atoms (C=O,N=O) undergo such
transitions.
 n ⇾ π* transitions require minimum energy and show absorption at longer wavelength
around 300 nm.
Ex: Carbonyl compounds.
1.2.4.LAWS OF ABSORPTION:-
Lambert’s Law
When a monochromatic radiation is passed through a solution, the decrease in the
intensity of radiation with thickness of the solution is directly proportional to the intensity of
the incident light.
Let I be the intensity of incident radiation.
x be the thickness of the solution. Then
dI
 I
dx
dI
So,   KI
dx
Integrate equation between limit I=I0 at x=0 and I=I at x=l,
We get,

Dr. KISHOR PALLE DEPT. OF CHEMISTRY ANURAG UNIVERSITY

Beer’s Law
When a monochromatic radiation is passed through a solution, the decrease in the
intensity of radiation with thickness of the solution is directly proportional to the intensity of
the incident light as well as concentration of the solution.
Let I- be the intensity of incident radiation.
x- be the thickness of the solution.
C -be the concentration of the solution. Then
dI
  C .I
dx
dI
So,   K .C.I
dx
Integrate equation between limit I=I0 at x=0 and I=I at x=l,
We get,

From the equation it is seen that the absorbance which is also called as optical density
(OD) of a solution in a container of fixed path length is directly proportional to the
concentration of a solution.

Dr. KISHOR PALLE DEPT. OF CHEMISTRY ANURAG UNIVERSITY

1.2.5.CONCEPT OF CHROMOPHORE AND AUXOCHROME:-
Chromophore
The part of a molecule responsible for imparting color, are called as chromophores.
(OR)
The functional groups containing multiple bonds capable of absorbing radiations above 200
nm due to n → π* & π → π* transitions.
e.g. NO2, N=O, C=O, C=N, C→N, C=C, C=S, etc.
 Non-conjugated alkenes show an intense absorption below 200 nm & are therefore
inaccessible to UV spectrophotometer.
 When double bonds are conjugated in a compound λmax is shifted to longer wavelength.

Auxochrome:-
The functional groups attached to a chromophore which modifies the ability of the
chromophore to absorb light, altering the wavelength or intensity of absorption.
(OR)
The functional group with non-bonding electrons that does not absorb radiation in near UV
region but when attached to a chromophore alters the wavelength & intensity of absorption.
Ex:- -OH, NH2, NR2, NHR, SH, OR, etc

1.2.6.ABSORPTION AND INTENSITY SHIFTS IN THE UV SPECTROSCOPY:-

There are four types of shifts observed in the UV spectroscopy

Dr. KISHOR PALLE DEPT. OF CHEMISTRY ANURAG UNIVERSITY

a) Bathochromic effect- This type of shift is also known as red shift. Bathochromic shift is an
effect by virtue of which the absorption maximum is shifted towards the longer wavelength
due to the presence of an auxochrome or change in solvents.The nonbonding to
pie* transition of carbonyl compounds observes bathochromic or red shift.

b) Hypsochromic shift- This effect is also known as blue shift. Hypsochromic shift is an effect
by virtue of which absorption maximum is shifted towards the shorter wavelength. Generally,
it is caused due to the removal of conjugation or by changing the polarity of the solvents.

c) Hyperchromic shift- Hyperchromic shift is an effect by virtue of which absorption

maximum increases. The introduction of an auxochrome in the compound generally results
in the hyperchromic effect.

d) Hypochromic shift- Hypochromic shift is defined as the effect by virtue of intensity of

absorption maximum decreases. Hypochromic shift occurs due to the distortion of the
geometry of the molecule with an introduction of new group.

Dr. KISHOR PALLE DEPT. OF CHEMISTRY ANURAG UNIVERSITY

1.2.7.SELECTION RULES FOR UV-VISIBLE SPECTROSCOPY
1. The transition of only one electron from lower electronic energy level to higher
electronic energy level by the absorption of UV-Visible radiation is allowed, means
provide more intense band. Transitions involving two or more electrons are forbidden
means provide less intense band or not detected.
2. π – π* transitions are allowed because π & π* orbitals are in plane; thus, they readily
overlap. n – π* transitions are forbidden because n & π* orbitals are out of plane. So, they
undergo poor overlapping.
3. Spin selection rule: During electronic transition retention of spin of electron is allowed.
Inversion of spin of electron is forbidden. Means ∆S = 0.
4. Angular momentum rule: The change in angular momentum should be 0 or ±1.
5. Multiplicity rule: Electron transition between the same spin multiplicity allowed (i.e.,
singlet to singlet or triplet to triplet), whereas, singlet to triplet or triplet to singlet is
forbidden.
6. Laporte rule: Electronic transitions involving molecular orbitals with same symmetry are
forbidden (less probable). Electronic transitions involving molecular orbitals with
different symmetry are highly probable.
Gerade (g) means molecular orbital having center of symmetry.
Ungerade (u) means the molecular orbital without center of symmetry.
i.e.,
allowed transitions: g → u or u → g
forbidden transitions: g → g or u →u
1.2.8.APPLICATIONS OF UV SPECTROSCOPY:-
1. Structure elucidation of organic compounds: UV-Visible absorption spectroscopy is
useful in the structure elucidation of organic compounds such as the presence or absence
of unsaturation or hetero atoms etc.
2. Detection of impurities: Impurities present in organic compounds can be detected by
UV-Visible absorption spectroscopy.
3. Detection of extent of conjugation- The extent of conjugation in the polyenes can be
detected with the help of UV spectroscopy. With the increase in double bonds the
absorption shifts towards the longer wavelength.
4. Identification of an unknown compound- An unknown compound can be identified with
the help of UV spectroscopy. The spectrum of unknown compound is compared with the
spectrum of a reference compound and if both the spectrums coincide then it confirms
the identification of the unknown substance.
5. Detection of functional groups: UV-Visible absorption spectroscopy is used to detect the
presence of certain functional groups present in compounds.
6. Detection of geometrical isomers (Trans and Cis): In the case of geometrical isomers,
trans isomers exhibit slightly longer wavelength than the corresponding cis isomers.

Dr. KISHOR PALLE DEPT. OF CHEMISTRY ANURAG UNIVERSITY

1.2.9.INFRARED (IR) [OR] VIBRATIONAL ROTATIONAL SPECTROSCOPY
 IR spectroscopy is the study of interaction between infrared radiations and matter.
 Infrared radiations refers broadly to that part of electromagnetic spectrum between
visible and microwave region.
 IR spectroscopy is an important analytical technique for determining the structure of
both inorganic & organic compounds.
 But it is particularly used to identify different functional groups present in organic
molecules.
 IR spectroscopy is also useful in molecular structure determination.
 The radiation sources used are incandescent lamp, Nernst glower etc., and the detectors
used are thermal and photon detectors.
Range: In terms of wavenumber IR region is from 12500 cm-1 to 50 cm-1. (The wavelength
region from 0.8 μm to 200 μm. But representation in wavelength is not common for IR
spectroscopy).
Near IR region: 12500 – 4000 cm-1 (0.8 – 2.5 μm).
Mid IR region: 4000 – 667 cm-1 (2.5 – 15 μm),
4000 – 1450 cm-1 is functional group region.
1450 – 667 cm-1 is fingerprint region.
Far IR region: 667 – 50 cm-1 (15 – 200 μm)
Mid IR region is the main important region. Almost all functional groups absorb in this
region.
1.2.10.PRINCIPLE OF IR SPECTROSCOPY:
 The principle of IR spectroscopy is related to the vibrational and rotational energy of a
molecule.
 When the frequency of the IR radiation is equal to the natural frequency of vibration,
the molecule absorb IR radiation and a peak is observed.
 Absorption of IR radiation causes an excitation of molecule from a lower to the higher
vibrational level.
 Each vibrational level is associated with a number of closely placed rotational level.
 Therefore the IR spectroscopy is also called as “vibrational-rotational spectroscopy”
 All the bonds in a molecule are not capable of absorbing IR energy but those bonds
which are accompanied by a change in dipole moment will absorb in the IR region and
such transitions are called IR active transitions.
 The transitions which are not accompanied by a change in dipole moment of the
molecule are not directly observed and are considered as IR inactive.
 In IR spectroscopy the changes in the vibrational energy depends upon
i. Mass of the atoms present in a molecule
ii. Strength of the bonds
iii. Arrangement of atoms within the molecule
 The bands correspond to the characteristic functional groups and the bonds present in a
chemical substance.
Dr. KISHOR PALLE DEPT. OF CHEMISTRY ANURAG UNIVERSITY
 Thus, an IR spectrum of a compound is considered as the fingerprint for its chemical
identification.
 There are 3 main process by which a molecule can absorb radiation, each of these route
involve an increase of energy which is proportional to the light absorbed.
i. First route occurs when absorption of radiation leads to a higher rotational
energy level in a rotational transition.
ii. Second occurs when absorption of radiation leads to a higher vibrational energy
level in a vibrational transition.
iii. Third occurs when absorption of radiation leads to a higher electronic energy
level in its electronic transitions.

1.2.11.SELECTION RULES OF IR SPECTROSCOPY:

 The most fundamental requirement for IR activity is that a vibration must cause change
in the dipole moment of the molecule. Means, the molecules which change their dipole
moments is IR active. Means the molecules having dipole moment is not equal to zero
then those molecules are IR active.
 If dipole moment is equal to zero then those molecules are IR inactive.
 Examples: HCl, NaOH, KOH, CHCl3, NH3, H2O, C2H5OH, H2S: μ ≠ 0, Therefore IR
active.
 The molecule which does not change their dipole moment during IR absorption is IR
inactive.
 Examples: H2, N2, Cl2, CH2=CH2, HC≡CH etc. are IR inactive.
Exception: Carbon dioxide (CO2) though it is a linear molecule and μ = 0, but it changes its
dipole moment due to asymmetric stretching and asymmetric bending hence it is IR active.
O=C=O
Asymmetric stretching (IR active)

Dr. KISHOR PALLE DEPT. OF CHEMISTRY ANURAG UNIVERSITY

1.2.12.MOLECULAR VIBRATIONS:
A Molecule may be regarded as system of balls (atoms) and springs (bonds) when it
absorbs IR radiation, vibrations can involve either changes in bond length (stretching) or
bond angle (bending). The following are different types of vibrations
1.Stretching vibrations: In this types of vibrations a change occurs in inter-atomic distance
along the bond axis. These are two types
i. Symmetric: In symmetric stretching vibration, both the atoms in a molecule either move
towards or away from the central atom, but in the same direction.

ii. Asymmetric: In asymmetric stretching vibration, one atom approach

towards the central atom, while the other atom goes away from the central atom.

2. Bending vibrations: In this type of vibrations, the position of atoms changes with respect to
the original bond axis. These are two types
i. In-plane bending: It is of again two types
a. Scissoring: In this type, two atoms approach each other.

b. Rocking: In this type, movement atoms takes place in the same direction.

ii. Out-of-plane bending: It is of again two types

a. Wagging: In this type, two atoms moves up and down the plane with respect to the central
atom.

Dr. KISHOR PALLE DEPT. OF CHEMISTRY ANURAG UNIVERSITY

b. Twisting: In this type, one of the atom moves up the plane, whereas the other moves down
the plane with respect to the central atom.

Calculation of no of molecular vibrations in molecules

For linear molecules: No of vibrations = 3N-5.
Where N is the number of atoms present in molecule.
Eg: 1) CO2: N = 3, 3x3-5 = 4 vibrations 2) BeCl2: N = 3, 3x3-5 = 4 vibrations.
3) HC≡CH: N = 4, 3x4-5 = 7 vibrations.
For non-linear molecules: No of vibrations = 3N-6.
Example: 1) NH3: N = 4, 3x4-6 = 6 vibrations.
2) H2O: N = 3, 3 x3-6 = 3. Therefore, water molecule has 3 vibrations.
1.2.13.APPLICATIONS OF IR SPECTROSCOPY:
1. Identification of functional groups & structure elucidation of organic compounds.
2. Quantitative analysis of a number of organic compounds.
3. Study of covalent bonds in molecules.
4. Studying the progress of reactions.
5. Detection of impurities in a compound.
6. Ratio of cis-trans isomers in a mixture of compounds.
7. Shape of symmetry of an inorganic molecule.
8. Study the presence of water in a sample.
9. Measurement of paints and varnishes.
1.2.14.LIMITATIONS OF IR SPECTROSCOPY:
1. Cannot determine the molecular weight of the compound.
2. Does not give information about the relative position of different functional groups in a
molecule.
3. From the single IR spectrum of an unknown substance, it is not possible to know
whether it is pure compound or a mixture of compound.
4. Sample cells are made of halaogen salts which are susceptible to moisture.
5. Gas samples cannot be analyzed as they lack sensitivity.
Dr. KISHOR PALLE DEPT. OF CHEMISTRY ANURAG UNIVERSITY